JP4562761B2 - Novel unsaturated group-containing polycarboxylic acid resin, resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a resist ink composition for a flexible printed wiring board and a cured product thereof. More specifically, it can be developed with a dilute alkaline aqueous solution that can be used for solder resists, plating resists, etc. in the production of flexible printed wiring boards, and its cured product has bending resistance, folding resistance, adhesion, chemical resistance, and heat resistance. The present invention relates to a composition suitable for a resist ink having excellent properties and the cured product thereof.

In recent years, ultraviolet curable compositions have been frequently used in various fields for reasons such as resource saving, energy saving, workability improvement, and productivity improvement. In the field of printed wiring board processing, various inks such as solder resist ink and marking ink have shifted from conventional thermosetting compositions to ultraviolet curable compositions for the same reason. For example, Japanese Patent Publication No. 56-40329 discloses a reaction product of an epoxy resin-photopolymerizable α, β-unsaturated carboxylic acid addition product and a dibasic carboxylic acid anhydride, a photopolymerizable monomer, and A curable photosensitive material containing a photopolymerization initiator is described. So far, the solder resist used for the polyimide substrate, which is said to be a flexible printed wiring board, is a type that can be applied with an adhesive after punching a polyimide film called a coverlay film with a mold that matches the pattern. UV curable type or thermosetting type solder resist ink was applied by a screen printing method. In general printed wiring boards called rigid (hard) boards, the demand for high accuracy and high resolution has been increasing for solder resists in order to achieve higher density as electronics advances. Since conventional screen printing methods do not provide pattern accuracy, a liquid photoresist method has been proposed and is currently introduced at 50% or more.
JP-A-49-54487 JP-A-8-301977

  In the field of flexible printed wiring boards, higher density has been demanded in recent years. However, with conventional liquid photo solder resists, pattern accuracy can be obtained, but the coating film is hard and has poor adhesion to polyimide, so sufficient flexibility. However, there is a problem that the workability is poor and the chemical resistance and heat resistance are insufficient.

  As a result of intensive research to solve the above problems, the present inventors can develop with a dilute alkaline aqueous solution by using a specific polycarboxylic acid resin, and the cured film is also flexible and resistant. The present inventors have found a resist ink composition for flexible printed wiring boards that has excellent foldability, adhesion, chemical resistance, heat resistance, and the like.

That is, the present invention
(1) A polyunsaturated polyol compound obtained by reacting an epoxy resin (a) having two epoxy groups in one molecule with a compound (b) having one unsaturated double bond and one carboxyl group in one molecule ( an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyol compound (d) other than c) and (c) with a compound (e) having two acid anhydride groups in one molecule,
(2) An unsaturated group-containing polycarboxylic acid resin (A) and a diluent (B) according to (1),
(3) The resin composition according to (2), comprising a photopolymerization initiator (C) and a curing component (D),
(4) The resin composition of (2) or (3), which is a printed wiring board resist,
(5) A cured product of the resin composition according to the above (2) to (4),
(6) An article having a layer of a cured product of the resin composition according to (5),
(7) The article according to (6), which is a printed wiring board,
About.

  The resist ink composition of the present invention is excellent in developability and photosensitivity in the formation of a solder resist pattern by selectively exposing with ultraviolet rays through a pattern-formed film and developing an unexposed portion. The cured product has excellent bending resistance and folding resistance, and sufficiently satisfies adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, etc. Especially, liquid solder resist ink for flexible printed circuit boards Suitable for the composition.

  The unsaturated group-containing polycarboxylic acid resin (A) of the present invention is an epoxy resin (a) having two epoxy groups in one molecule, and a mono having one unsaturated double bond and one carboxyl group in one molecule. A polyunsaturated polyol compound (c) reacted with a carboxylic acid compound (b), a polyol compound (d) other than (c), and a compound (e) having two acid anhydride groups in one molecule are reacted. Can be obtained.

  Specifically, in the first reaction, a hydroxyl group is formed by an addition reaction between the epoxy residue of the epoxy resin (a) and the carboxyl residue of the monocarboxylic acid (b) to obtain the component (c). Next, it is presumed that the hydroxyl groups of (c) and (d) are esterified with the compound (e) having two acid anhydride groups in one molecule.

As an epoxy resin (a) which has two epoxy groups in 1 molecule, a diglycidyl ether compound, a diglycidyl ester compound, a diglycidyldiamine compound etc. are mentioned, for example.
The diglycidyl ether compound is obtained by reacting a polyol compound and epichlorohydrin by adding 1 equivalent or more of the latter to 1 equivalent of the former hydroxyl group. Examples of the polyol compound include bisphenol A, bisphenol F, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, resorcinol, biphenol, tetramethylbiphenol, tetraalkylbiphenol, hydrogenated bisphenol A, hydrogenated bisphenol. F, tetrabromobisphenol A, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, 1 , 9-nonanediol, 1,4-hexanedimethanol, dimer acid diol and the like.

  The diglycidyl ester compound can be obtained by adding a polycarboxyl compound and epichlorohydrin at least 1 equivalent of the latter to 1 equivalent of the former carboxyl group and reacting them. Examples of the polycarboxyl compound include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, succinic acid, maleic acid and the like. Moreover, a diglycidyldiamine compound is obtained by adding a polyamino compound and epichlorohydrin at least 1 equivalent of the latter to 1 equivalent of the former amino group and reacting them. Examples of the polyamino compound include aniline and o-toluidine.

  Next, examples of the unsaturated group-containing monocarboxylic acid (b) include acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or unsaturated dibasic acid and unsaturated group-containing monoglycidyl compound. These reactants can be mentioned. Examples of acrylic acids include dimers of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated or unsaturated dibasic acid anhydride, and one hydroxyl group in one molecule. Examples include half-esters that are equimolar reactants with (meth) acrylate derivatives, and half-esters that are equimolar reactants of saturated or unsaturated dibasic acid with monoglycidyl (meth) acrylate derivatives.

  Examples of saturated or unsaturated dibasic acid anhydrides used in the production of half esters include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl Examples thereof include tetrahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride and the like. Examples of (meth) acrylate derivatives having one hydroxyl group in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, (meth) acrylate of phenylglycidyl ether, and the like.

  In addition, examples of saturated or unsaturated dibasic acids used in the production of other half esters include succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid, and fumaric acid. Examples of monoglycidyl (meth) acrylate derivatives include glycidyl (meth) acrylate.

  These unsaturated group-containing monocarboxylic acids (b) can be used alone or in combination. A particularly preferred monocarboxylic acid is (meth) acrylic acid.

  In order to obtain the polyunsaturated polyol compound (c), the unsaturated group-containing monocarboxylic acid (b), about 0.8 to 1.3 mol, per 1 equivalent of the epoxy group of the epoxy resin (a). The reaction is preferably performed at a ratio of about 0.9 to 1.1 mol.

  During the reaction, as diluents, ketones such as ethyl methyl ketone and cyclohexane, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, glycol ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether, ethyl acetate Organic solvents such as esters such as butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, or Carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (hydroxyethyl) iso Anuretotori (meth) acrylate, preferably used reactive monomers such as dipentaerythritol hexa (meth) acrylate.

  Furthermore, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst include triethylamine, pendyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octoate, and zirconium octoate. The amount of the catalyst used is preferably 0.1 to 10% by weight based on the reaction raw material mixture. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like. The amount used is preferably 0.01 to 1% by weight with respect to the reaction raw material mixture. The reaction temperature is preferably 60 to 150 ° C. The reaction time is preferably 5 to 60 hours.

  Examples of the polyol compound (d) other than (c) used in the present invention include alkyl polyol, polyester polyol, polyether polyol, polybutadiene polyol, phenolic polyol, flame retardant polyol, silicone polyol and / or urethane polyol. .

  Examples of the alkyl polyol include 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, 1,9-nonanediol, 1,4-hexanedimethanol, dimer acid Examples thereof include diol and dimethylolpropionic acid.

  Examples of the polyester polyol include condensation-type polyester polyol, addition-polymerized polyester polyol, and polycarbonate polyol. Examples of the condensed polyester polyol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, 1,9-nonanediol, By condensation reaction of diol compounds such as 1,4-hexanedimethanol, dimer acid diol, and polyethylene glycol with organic polybasic acids such as adipic acid, isophthalic acid, terephthalic acid, sebacic acid, pyromellitic acid, and ethylene glycol bistrimellitate The molecular weight obtained is preferably 100 to 100,000.

  Examples of the addition polymerization polyester polyol include polycaprolactone, and the molecular weight is preferably from 100 to 100,000. Polycarbonate polyol is synthesized by direct phosgenation of polyol, transesterification with diphenyl carbonate, and the like, and the molecular weight is preferably 100 to 100,000.

  Examples of polyether polyols include PEG, PPG, and PTG polyols. The PEG-based polyol is obtained by addition polymerization of ethylene oxide using a compound having active hydrogen as a reaction initiator, and the molecular weight is preferably 100 to 100,000. The PPG polyol is obtained by addition polymerization of propylene oxide using a compound having active hydrogen as a reaction initiator, and the molecular weight is preferably 100 to 100,000. The PTG-based polyol is synthesized by cationic polymerization of tetrahydrofuran, and the molecular weight is preferably 100 to 100,000.

  Examples of polyether polyols other than the above polyether polyols include ethylene oxide adducts or propylene oxide adducts of bisphenol A, and the molecular weight is preferably 100 to 100,000.

  Other polyols include polybutadiene polyols, which are butadiene copolymers and have a hydroxyl group at the end, phenolic polyols containing phenol molecules in the molecule, flame retardants containing phosphorus atoms, halogen atoms, etc. Examples thereof include a polyol and a silicone polyol having a siloxane bond, and the molecular weight is preferably from 100 to 100,000. These polyol compounds can be used individually or in mixture of 2 or more types.

  Examples of the urethane polyol include a reaction product of the above polyol compound and a polyisocyanate compound. Examples of the polyisocyanate compound include 2,4- and / or 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI). ), Polymeric MDI, 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, hydrogenated MDI, lysine diisocyanate, Etc. These polyisocyanate compounds can be used alone or in admixture of two or more.

  The isocyanate group of the polyisocyanate compound is preferably reacted in an amount of 0.5 to less than 1.0 equivalent to 1 equivalent of the hydroxyl group of the polyol compound. This urethanization reaction can be carried out by a known method, and the reaction temperature is usually from room temperature to 100 ° C, preferably from 50 to 90 ° C. Although the reaction of these hydroxyl groups and isocyanate groups proceeds without a catalyst, for example, a catalyst such as triethylamine, dibutyltin laurate or dibutyltin diacetate may be added.

  Examples of the compound (e) having two acid anhydride groups in one molecule include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, Examples thereof include diphenyl sulfone tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, ethylene glycol bis (anhydro trimellitate) and the like.

  Next, the reaction of the polyunsaturated polyol compounds (c) and (d) and the compound (e) having two acid anhydride groups in one molecule is the sum of the polyol compounds (c) and (d). It is preferable to react 0.1 to 0.9 equivalent of the compound (e) having two acid anhydride groups in one molecule per equivalent of the hydroxyl group. The reaction temperature is preferably 60 to 150 ° C., the reaction time is preferably 1 to 10 hours, and a catalyst such as triethylamine may be added in an amount of 0.1 to 10%.

  The acid value (mgKOH / g) of the unsaturated group-containing polycarboxylic acid resin (A) thus obtained is preferably from 30 to 200, particularly preferably from 50 to 150.

  The resin composition of the present invention contains an unsaturated group-containing polycarboxylic acid (A) and a diluent (B). The amount of the unsaturated group-containing polycarboxylic acid (A) contained in this resin composition is preferably 10 to 80% by weight, particularly preferably 15 to 75% by weight, in the composition.

  As the diluent (B), for example, an organic solvent and / or a photopolymerizable monomer can be used. Typical organic solvents include, for example, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene. Glycol ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethanol, propanol, Alcohols such as ethylene glycol and propylene glycol, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphth , It may be mentioned petroleum-based solvents such as solvent naphtha.

  On the other hand, representative photopolymerizable monomers include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol, methoxytetraethylene glycol, polyethylene Glycol mono- or di (meth) acrylates such as glycol, N, N-dimethyl (meth) acrylamide, (meth) acrylamides such as N-methylol (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate Polyalkyl alcohols such as aminoalkyl (meth) acrylates such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate Or ethylene oxide or propylene oxide adducts of phenols such as polyvalent (meth) acrylates, phenoxyethyl (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, etc. (Meth) acrylates, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, glycidyl ether (meth) acrylates such as triglycidyl isocyanurate, ε-caprolactone modified (meta) such as caprolactone-modified tris (acryloxyethyl) isocyanurate ) Acrylates and melamine (meth) acrylates.

  The diluent (B) is used alone or as a mixture of two or more, and the amount of the diluent (B) contained in the composition of the present invention is preferably 5 to 80% by weight, particularly preferably in the composition. Is from 10 to 70% by weight.

  The purpose of use of the diluent (B) is, in the case of a photopolymerizable monomer, to dilute the component (A) to make it easy to apply and to enhance the photopolymerizability. The component (A) is dissolved and diluted, whereby it is applied as a liquid and then dried to form a film more. Therefore, depending on the diluent used, either a contact method or a non-contact exposure method in which the photomask is brought into contact with the coating film is used.

  The resin composition of the present invention may contain a photopolymerization initiator (C). Examples of the photopolymerization initiator (C) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1 , 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, acetophenones such as N, N-dimethylaminoacetophenone, Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4-dimethylthioxanthate Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4 , 4'-bisdiethylaminobenzophenone, Michler's ketone, benzophenones such as 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc., used alone or in combination of two or more Can do.

  A preferred combination is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (Ciba Geigy, Irgacure 907) and 2,4-diethylthioxanthone (Nippon Kayaku) (Commercially available, Kayacure DETX), 2-isopropylthioxanthone or 4-benzoyl-4'-methyldiphenyl sulfide.

  The use ratio of the photopolymerization initiator (C) is preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, in the nonvolatile component of the resin composition of the present invention.

  Further, the photopolymerization initiator (C) includes N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl 4-dimethylaminobenzoate, triethylamine, triethanolamine and the like tertiary. Photosensitizers such as amines can be used alone or in combination of two or more. The usage-amount is about 0.1 to 20 weight% in the non-volatile component of a resin composition.

  Examples of the curing component (D) include those that do not have an unsaturated double bond and that themselves are cured by heat, ultraviolet rays, or the like, and the hydroxyl group or carboxyl of the component (A) that is the main component in the composition of the present invention. It may be one that reacts with a group or the like by heat or ultraviolet rays. The purpose of use of the curing component (D) is to improve various properties as a solder resist such as adhesion, heat resistance and plating resistance.

  Examples of the curing component (D) include epoxy compounds having one or more epoxy groups in one molecule, melamine derivatives such as hexamethoxymelamine, hexabutoxylated melamine, condensed hexamethoxymelamine, compounds such as dimethylolurea, tetramethylol, and the like. -Bisphenol A compounds, such as bisphenol A, an oxazoline compound, etc. can be mentioned.

  Examples of epoxy compounds having one or more epoxy groups in one molecule include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol A type epoxy resins, and bisphenol A novolacs. Type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, alicyclic epoxy resin, and the like.

  As the bisphenol A type epoxy resin, for example, manufactured by Yuka Shell Co., Ltd., Epicoat 1009, 1031, manufactured by Dainippon Ink & Chemicals, Inc., Epicron N-3050, N-7050, manufactured by Dow Chemical Co., Ltd., DER- 642U, DER-673MF and the like. Examples of the hydrogenated bisphenol A type epoxy resin include ST-2004, ST-2007 and the like manufactured by Toto Kasei Co., Ltd. Examples of the bisphenol F type epoxy resin include YDF-2004, YDF-2007, etc. manufactured by Tohto Kasei Co., Ltd. Examples of the brominated bisphenol A type epoxy resin include Sakamoto Yakuhin Kogyo Co., Ltd., SR-BBS, SR-TBA-400, Toto Kasei Co., Ltd., YDB-600, YDB-715 and the like.

  Moreover, as a novolak-type epoxy resin, Nippon Kayaku Co., Ltd. make, EPPN-201, EOCN-103, EOCN-1020, BREN etc. are mention | raise | lifted, for example. Examples of the bisphenol A novolak type epoxy resin include Dainippon Ink & Chemicals, Inc. and Epicron N-880. Examples of the amino group-containing epoxy resin include YL-931 and YL-933 manufactured by Yuka Shell Co., Ltd. Examples of the rubber-modified epoxy resin include Dainippon Ink & Chemicals, Inc., Epicron TSR-601, ACR, R-1415-1, and the like. Examples of the bisphenol S type epoxy resin include Nippon Kayaku Co., Ltd., EBPS-200, Dainippon Ink & Chemicals, Inc., and Epicron EXA-1514. Examples of the bixylenol type epoxy resin include diglycidyl terephthalate such as Plenmer DGT, triglycidyl isocyanurate such as TEPIC, manufactured by Nippon Oil & Fats Co., Ltd., YX-4000 manufactured by Yuka Shell Co., Ltd. Etc. Examples of the alicyclic epoxy resin include bisphenol type epoxy resins such as YL-6056 manufactured by Yuka Shell Co., Ltd., Daicel Chemical Industries, Celoxide 2021, and the like.

  The curing component (D) is used alone or as a mixture of two or more, and the amount of the curing component (D) contained in the composition of the present invention is preferably 1 to 50% by weight, particularly preferably. Is from 3 to 45% by weight.

  When an epoxy compound is used in the curing component (D), an epoxy resin curing agent or curing accelerator may be used in combination in order to further improve properties such as adhesion, chemical resistance, and heat resistance. preferable. These epoxy resin curing agents and curing accelerators can be used alone or in combination of two or more. The amount of the epoxy resin curing agent used is preferably 0.01 to 25 parts by weight, particularly preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the epoxy compound. Curing accelerators are appropriately used as necessary.

  Examples of the epoxy resin curing agent include imidazole derivatives, guanamines such as acetoguanamine and benzoguanamine, polyamines and their organic acid salts and / or epoxy adducts, boron trifluoride amine complexes, triazine derivatives, tertiary amines, Polyphenols, polybasic acid anhydrides, styrene-maleic anhydride resins, equimolar reaction products of phenyl isocyanate and dimethylamine, and equimolar reaction products of organic polyisocyanate such as tolylene diisocyanate and isophorone diisocyanate and dimethylamine can give.

  Examples of imidazole derivatives include 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, manufactured by Shikoku Kasei Kogyo Co., Ltd. 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ and the like. Examples of polyamines include diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide and the like. Examples of the triazine derivative include ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine and the like. Examples of the tertiary amines include trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris. (Dimethylaminophenol), tetramethylguanidine, m-aminophenol and the like. Examples of polyphenols include polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak, and the like.

  Examples of curing accelerators include organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine, tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, and the like. Quaternary ammonium salts such as phosphonium salts, benzyltrimethylammonium chloride, phenyltributylammonium chloride, diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, ciba -Photocationic polymerization catalysts such as those manufactured by Geigy, Irgacure 261, manufactured by Asahi Denka Co., Ltd., and Optomer SP-170.

  The composition of the present invention may further comprise barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, as necessary for the purpose of improving properties such as adhesion and hardness. Inorganic fillers such as magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder can be used. The amount to be used is preferably 0 to 60% by weight, particularly preferably 5 to 40% by weight in the composition of the present invention.

  Furthermore, if necessary, colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol , Polymerization inhibitors such as phenothiazine, thickeners such as asbestos, olben, benton, montmorillonite, antifoaming agents and / or leveling agents such as silicones, fluorines, polymers, etc., imidazoles, thiazoles, triazoles Additives such as adhesion imparting agents such as silane coupling agents can be used.

  Also, binder resins such as copolymers of ethylenically unsaturated compounds such as acrylic esters, polyester resins synthesized from polyhydric alcohols and polybasic acid compounds, polyester (meth) acrylates, polyurethane (meta ) Photopolymerizable oligomers such as acrylate and epoxy (meth) acrylate can also be used as long as they do not affect the properties of the solder resist.

  Water can also be added to reduce the flammability of the composition of the present invention. In the case of adding water, the carboxyl group of component (A) is converted to amines such as trimethylamine and triethylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, By salting with a (meth) acrylate compound having a tertiary amino group such as N-dimethyl (meth) acrylamide, acryloylmorpholine, N-isopropyl (meth) acrylamide, N-methylolacrylamide, the component (A) is made into water. It is preferable to dissolve.

  The composition of the present invention is obtained by blending the above blending components preferably in the above proportions and uniformly mixing with a roll mill or the like.

  The composition of the present invention is liquid and is useful as a resist ink, and can also be used as a paint, a coating agent, an adhesive, and the like.

  The cured product of the present invention is obtained by curing the above resin composition of the present invention by irradiation with actinic rays such as ultraviolet rays. Curing by irradiation with actinic rays such as ultraviolet rays can be performed by a conventional method. For example, in the case of irradiating ultraviolet rays, an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser (such as an excimer laser) may be used. The cured product of the resin composition of the present invention is used, for example, in an electrical / electronic component such as a printed circuit board as a permanent resist or an interlayer insulating material for a build-up method. The thickness of the cured product layer is about 0.5 to 160 μm, preferably about 1 to 60 μm.

  The printed wiring board of the present invention can be obtained, for example, as follows. That is, the composition of the present invention is adjusted to a viscosity suitable for the coating method as required, for example, on a flexible printed wiring board formed with a circuit, a screen printing method, a spray method, a roll coating method, an electrostatic coating method, After applying the composition of the present invention in a film thickness of 0.5 to 160 μm, preferably 1 to 60 μm by a method such as curtain coating, and drying the coating film at 60 to 110 ° C., the negative film is applied to the coating film. Directly contact (or place on the coating without contact), then irradiate with actinic rays, and dissolve and remove unexposed parts with dilute alkaline aqueous solution (for example, 0.5-2% sodium carbonate aqueous solution) After (development), in order to further improve physical properties, the cured film is sufficiently cured by irradiation with actinic rays and / or heating (for example, at 100 to 200 ° C., for 0.5 to 1.0 hour). obtain. Thereby, various characteristics, such as the heat resistance of the resist film excellent in flexibility, solvent resistance, acid resistance, adhesiveness, an electrical property, can be improved. Examples of the active light include ultraviolet light and visible light. Examples of the active light source include a low-pressure or high-pressure mercury lamp and a xenon lamp.

  Examples of the alkaline aqueous solution used for development include dilute alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines. As the irradiation light source for photocuring, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp is suitable. In addition, a laser beam or the like can also be used as the exposure active light.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the part in an Example is a weight part.

Synthesis example 1
In a round bottom flask equipped with a stirrer and a cooling tube, 500 g of bisphenol F type epoxy resin (product name YDF-8170C, manufactured by Tohto Kasei Co., Ltd.), 224.2 g of acrylic acid, 3.62 g of triphenylphosphine, and methoxyphenol 0 .72 g was charged, heated to 60 ° C. and dissolved, and then reacted at 98 ° C. for 24 hours. Next, 36.21 g of silicone polyol (product name FZ-3722, manufactured by Nippon Unicar Co., Ltd.), ethylene glycol bis (anhydro trimellitate), 423 g (TMEG-200, manufactured by Shin Nippon Rika Co., Ltd.), carbitol acetate 788.9 g was added and reacted at 98 ° C. for 24 hours to obtain an unsaturated group-containing polycarboxylic acid resin (A-1) having an acid value of 94.3 mgKOH / g.

Synthesis example 2
In a round bottom flask equipped with a stirrer and a cooling tube, 500 g of bisphenol A type epoxy resin (product name YD-8125, manufactured by Tohto Kasei Co., Ltd.), 206.8 g of acrylic acid, 3.53 g of triphenylphosphine, and methoxyphenol 0 .71 g was charged, heated to 60 ° C. and dissolved, and then reacted at 98 ° C. for 24 hours. Next, 35.34 g of silicone polyol (product name FZ-3722, manufactured by Nihon Unicar Co., Ltd.), ethylene glycol bis (anhydro trimellitate), (TMEG-200, manufactured by Shin Nippon Rika Co., Ltd.) 477.9 g, Calvi 693.4 g of tall acetate was added and reacted at 98 ° C. for 24 hours to obtain an unsaturated group-containing polycarboxylic acid resin (A-2) having an acid value of 110.4 mg KOH / g.

Synthesis example 3
In a round bottom flask equipped with a stirrer and a condenser tube, 500 g of tetramethylbiphenol diglycidyl ether (product name YX-4000, manufactured by Yuka Shell Epoxy Co., Ltd.), 187.7 g of acrylic acid, 3.44 g of triphenylphosphine, 0.68 g of methoxyphenol was charged, heated to 60 ° C. and dissolved, and then reacted at 98 ° C. for 24 hours. Subsequently, 34.4 g of silicone polyol (product name FZ-3722, manufactured by Nihon Unicar Co., Ltd.), 193.6 g of pyromellitic anhydride (PMDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 392.4 g of carbitol acetate were added, and 98 It was made to react at 24 degreeC for 24 hours, and the acid value 108.8mgKOH / g unsaturated group containing polycarboxylic acid resin (A-3) was obtained.

Synthesis example 4
In a round bottom flask equipped with a stirrer and a condenser tube, 188 g of tetramethylbiphenol diglycidyl ether (product name YX-4000, manufactured by Yuka Shell Epoxy Co., Ltd.), 72.06 g of acrylic acid, 1.3 g of triphenylphosphine, 0.26 g of methoxyphenol was charged, heated to 60 ° C. and dissolved, and then reacted at 98 ° C. for 24 hours. Subsequently, 13.0 g of a reaction product of 1 mol of hexamethylene diisocyanate and 2 mol of 1,6-hexanediol, ethylene glycol bis (anhydrotrimellitate), (TMEG-200, manufactured by Shin Nippon Rika Co., Ltd.), 127.9 g Then, 267.3 g of carbitol acetate was added and reacted at 98 ° C. for 24 hours to obtain an unsaturated group-containing polycarboxylic acid resin (A-4) having an acid value of 90.2 mgKOH / g.

Synthesis example 5
In a round bottom flask equipped with a stirrer and a cooling tube, 168.2 g of bisphenol A type epoxy tree (manufactured by Co., Ltd.), 72.06 g of acrylic acid, 1.2 g of triphenylphosphine, and 0.24 g of methoxyphenol The mixture was charged, heated to 60 ° C., dissolved, and then reacted at 98 ° C. for 24 hours. Next, 12.0 g of 1,9-nonanediol, 118.9 g of pyromellitic anhydride (PMDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 244.1 g of carbitol acetate were added and reacted at 98 ° C. for 24 hours. 165.6 mgKOH / g of unsaturated group-containing polycarboxylic acid resin (A-5) was obtained.

Synthesis Example 6
In a round bottom flask equipped with a stirrer and a cooling tube, a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (product name ZX-1059, manufactured by Tohto Kasei Co., Ltd.) 168.2 g, acrylic acid 72.06 g, tri 1.2 g of phenylphosphine and 0.24 g of methoxyphenol were charged, heated to 60 ° C. and dissolved, and then reacted at 98 ° C. for 24 hours. Subsequently, 12.0 g of polytetramethylene glycol (product name PTG-650SN, manufactured by Hodogaya Chemical Co., Ltd.), 111.5 g of pyromellitic anhydride (PMDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 242.5 g of carbitol acetate In addition, the mixture was reacted at 98 ° C. for 24 hours to obtain an unsaturated group-containing polycarboxylic acid resin (A-6) having an acid value of 163.1 mg KOH / g.

Synthesis example 7
In a round bottom flask equipped with a stirrer and a cooling tube, a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (product name ZX-1059, manufactured by Tohto Kasei Co., Ltd.) 168.2 g, acrylic acid 72.06 g, tri 1.2 g of phenylphosphine and 0.24 g of methoxyphenol were charged, heated to 60 ° C. and dissolved, and then reacted at 98 ° C. for 24 hours. Next, 12.0 g of 3-methyl-1,5-pentanediol adipate, 113.6 g of pyromellitic anhydride (PMDA, manufactured by Mitsubishi Gas Chemical Co., Inc.), 238.9 g of carbitol acetate are added, and the mixture is heated at 98 ° C. for 24 hours. By reacting, an unsaturated group-containing polycarboxylic acid resin (A-7) having an acid value of 163.1 mg KOH / g was obtained.

Synthesis example 8
In a round bottom flask equipped with a stirrer and a cooling tube, a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (product name ZX-1059, manufactured by Tohto Kasei Co., Ltd.) 168.2 g, acrylic acid 72.06 g, tri 1.2 g of phenylphosphine and 0.24 g of methoxyphenol were charged, heated to 60 ° C. and dissolved, and then reacted at 98 ° C. for 24 hours. Next, 1,2-polybutadiene glycol (product name NISSO-PB G-2000, manufactured by Nippon Soda Co., Ltd.) 12.0 g, pyromellitic anhydride (PMDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 109.8 g, carbitol acetate 233.9g was added and it was made to react at 98 degreeC for 24 hours, and the acid value 161.0mgKOH / g unsaturated group containing polycarboxylic acid resin (A-8) was obtained.

Synthesis Example 9
In a round bottom flask equipped with a stirrer and a condenser, tetrahydrophthalic acid diglycidyl ether (product name AK601, manufactured by Nippon Kayaku Co., Ltd.) 150.0 g, acrylic acid 72.06 g, triphenylphosphine 1.11 g, methoxy 0.22 g of phenol was charged, heated to 60 ° C. and dissolved, and then reacted at 98 ° C. for 24 hours. Next, 11.1 g of silicone polyol (product name FZ-3722, manufactured by Nippon Unicar Co., Ltd.), ethylene glycol bis (anhydrotrimellitate), (TMEG-200, manufactured by Shin Nippon Rika Co., Ltd.) 208.9 g, Calvi 294.7 g of tall acetate was added and reacted at 98 ° C. for 24 hours to obtain an unsaturated group-containing polycarboxylic acid resin (A-9) having an acid value of 129.3 mgKOH / g.

Examples 1-7, Comparative Examples 1-2
The composition was blended according to the blending composition shown in Table 1 (the numerical value is parts by weight), and kneaded with a three-roll mill. This is applied by screen printing to a copper-clad polyimide film substrate (copper thickness / 12μm / polyimide film thickness / 25μm) patterned to a thickness of 20-30μm using a 100 mesh polyester screen. The coating film was dried with a hot air dryer at 80 ° C. for 30 minutes. Next, a negative film having a resist pattern was brought into close contact with the coating film and irradiated with ultraviolet rays using an ultraviolet exposure apparatus (Oak Seisakusho, model HMW-680GW) (exposure amount: 500 mJ / cm ² ). Next, development was performed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² to dissolve and remove unexposed portions. The obtained product was evaluated for developability and photosensitivity as described later. Then, heat curing for 40 minutes in a hot air dryer at 150 ° C., about the test piece having the obtained cured film, as described later, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, bending resistance, A folding resistance test was performed. The results are shown in Table 1. The test method and evaluation method are as follows.

(Developability)
The following evaluation criteria were used.
○ ···························· Ink was completely removed and developed during development

(Light sensitivity)
Stepped tablet 21 steps (made by Stoffer) were brought into close contact with the dried coating film and irradiated with ultraviolet rays with an integrated light amount of 500 mJ / cm ² . Next, the film was developed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the number of coating layers remaining without development was confirmed.
○ ・ ・ ・ ・ 9 steps or more △ ・ ・ ・ ・ 6 to 8 steps × ・ ・ ・ ・ 5 steps or less

(Adhesion)
In accordance with JIS K5400, 100 test pieces of 1 mm size were made and a peeling test was performed using cello tape (registered trademark), and the peeled state of the size was observed and evaluated according to the following criteria.
○ ········ 100/100 with no peeling Δ ······· 50/100 to 99/100
× ... 0/100 to 49/100

(Pencil hardness)
Evaluation was performed according to JIS K5400.

(Solvent resistance)
The test piece was immersed in isopropyl alcohol for 30 minutes at room temperature. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ··· No abnormal appearance on coating film, no blistering or peeling × ···· Falling or peeling on coating film

(Acid resistance)
The test piece was immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ・ ・ ・ ・ No abnormalities in the appearance of the coating film and no swelling or peeling × ・ ・ ・ ・ A coating film with swelling or peeling

(Heat-resistant)
A rosin flux was applied to the test piece and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as 1 cycle and repeated 3 cycles. After being allowed to cool to room temperature, a peeling test with Cellotape (registered trademark) was conducted, and the following criteria were evaluated.
○ ··· No abnormal appearance on coating film, no blistering or peeling × ···· Falling or peeling on coating film

(Flexibility)
This was performed according to JIS K5400. Using the test piece, the diameter of the mandrel was 2 mm, and the presence or absence of cracks was observed.
○ ・ ・ ・ ・ No cracks.
× ····· A crack occurred in the bent portion and the cured film was peeled off.

(Folding resistance)
This was performed according to JIS K5016. The radius of curvature of the bent surface was 0.38 mm, and the number of times of bending until a crack occurred was measured.
○ ・ ・ ・ ・ 1000 times or more × ・ ・ ・ ・ ・ ・ 1 time

note)
1) KAYARAD ZBR-: Nippon Kayaku Co., Ltd., bisphenol A type epoxy acrylate (manufactured by Yuka Shell Epoxy Co., Ltd., made by reacting acrylic acid with Epicoat 1004) and succinic anhydride , 24.5% by weight of carbitol acetate and 10.5% by weight of solvent naphtha, and the acid value of the solid content is 100 mgKOH / g

* 2) KAYARAD PCR-: Nippon Kayaku Co., Ltd., phenol novolac epoxy acrylate (Nippon Kayaku Co., Ltd., EPPN-201 reacted with acrylic acid) and succinic anhydride In which 24.5% by weight of carbitol acetate and 10.5% by weight of solvent naphtha are contained, and the acid value of the solid content is 100 mgKOH / g

* 3) U-200AX: Shin-Nakamura Chemical Co., Ltd., urethane acrylate * 4) M-325: Toa Gosei Chemical Co., Ltd., caprolactone-modified tris (acryloxyethyl) isocyanurate * 5) KAYARAD DPHA: Nippon Kayaku Co., Ltd., Dipentaerythritol penta and hexaacrylate mixture * 6) Irgacure 907: Ciba Geigy, photopolymerization initiator, 2-methyl- [4- (methylthio) phenyl] -2- Morpholino-1-propanone * 7) KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator, 2,4-diethylthioxanthone

* 8) KAYACURE BMS: manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator, 4-benzoyl-4′-methylphenyl sulfide * 9) R-1415-1: manufactured by ARC Corporation, rubber modified Epoxy resin * 10) EXA-4800: manufactured by Dainippon Ink Industries, Ltd., bisphenol S type epoxy resin * 11) Aerosil # 200: manufactured by Nippon Aerosil Co., Ltd., anhydrous silica * 12) Modaflow: manufactured by Monsanto Co., Ltd. Leveling agent

  As is clear from the evaluation results in Table 1, the resist ink composition of the present invention and its cured product are excellent in developability and photosensitivity, and the cured product has bending resistance, folding resistance, solvent resistance, and acid resistance. It is clear that it has excellent properties and heat resistance.

Claims (4)

A polyunsaturated polyol compound (a) obtained by reacting an epoxy resin (a) having two epoxy groups in one molecule with a compound (b) having one unsaturated double bond and one carboxyl group in one molecule ( c) and 1,9-nonanediol as a polyol compound (d) other than (c), a polyether polyol, a polyester polyol, a polybutadiene polyol, a silicone polyol and / or a urethane polyol synthesized by cationic polymerization of tetrahydrofuran; An unsaturated group-containing polycarboxylic acid resin (A) obtained by a production method characterized by reacting a compound (e) having two acid anhydride groups in the molecule at 60 to 150 ° C. and a diluent (B ) Containing a resin composition for resists of printed wiring boards. Further, the photopolymerization initiator (C) and the resist resin composition of the printed wiring board according to claim 1, characterized in that a curing component (D). A method for producing a cured product of a resin composition for resist for printed wiring boards, wherein the resin composition according to claim 1 or 2 is irradiated with actinic rays. The printed wiring board which has the layer of the hardened | cured material of the resin composition obtained by the manufacturing method of Claim 3 .